US6087423A - 1-hydroxydihydrophosphole oxides and 1-hydroxy-phospholane oxides, preparation thereof and use thereof as flame retardants - Google Patents

1-hydroxydihydrophosphole oxides and 1-hydroxy-phospholane oxides, preparation thereof and use thereof as flame retardants Download PDF

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Publication number
US6087423A
US6087423A US08/810,656 US81065697A US6087423A US 6087423 A US6087423 A US 6087423A US 81065697 A US81065697 A US 81065697A US 6087423 A US6087423 A US 6087423A
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US
United States
Prior art keywords
aluminum
oxide
compound
hydroxy
polymer
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Expired - Fee Related
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US08/810,656
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English (en)
Inventor
Hans-Jerg Kleiner
Winfried Budzinsky
Gunther Kirsch
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Ticona GmbH
Aventis Research and Technologies GmbH and Co KG
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Ticona GmbH
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Assigned to HOECHST AKTIENGESELLSCHAFT reassignment HOECHST AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BUDZINSKY, WINFRIED, KIRSCH, GUNTHER, KLEINER, HANS-JERG
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Assigned to TICONA GMBH reassignment TICONA GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AVENTIS RESEARCH & TECHNOLOGIES GMBH & CO. KG
Assigned to HOECHST RESEARCH & TECHNOLOGY DEUTSCHLAND GMBH & CO. KG reassignment HOECHST RESEARCH & TECHNOLOGY DEUTSCHLAND GMBH & CO. KG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HOECHST AKTIENGESELLSCHAFT
Assigned to AVENTIS RESEARCH & TECHNOLGIES GMBH & CO. KG reassignment AVENTIS RESEARCH & TECHNOLGIES GMBH & CO. KG CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: HOESCHST RESEARCH & TECHNOLOGY DEUTSCHLAND GMBH & CO. KG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
    • C07F9/65681—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms the ring phosphorus atom being part of a (thio)phosphinic acid or ester thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

Definitions

  • Polymers are frequently rendered flame-resistive by adding phosphorus and halogen compounds or mixtures thereof to them. Some polymers are processed at high temperatures, for example at 250° C. or higher. For this reason, many known flame retardants are unsuitable for such applications, since they are too volatile or are not sufficiently heat-resistant.
  • Alkali metal salts of phosphinic acids are known as flame-retardant additives for polyamide molding materials (DE-A1-2 447 727). However, they tend to exhibit corrosion effects.
  • the flame retardants shall be simple and inexpensive to prepare and possess good flame retardancy and also high temperature resistance (e.g. resistance to temperatures of at least 250° C.).
  • salts of 1-hydroxydihydrophosphole oxides and/or 1-hydroxyphospholane oxides possess excellent flame retardancy in thermoplastic polymers such as polyamides or polyesters.
  • the present invention accordingly provides salts of 1-hydroxydihydrophosphole oxides and/or 1-hydroxyphospholane oxides, processes for preparing them and their use as flame retardants.
  • the present invention further provides molding materials comprising a plastic (preferably a thermoplastic) and at least one salt of a 1-hydroxydihydrophosphole oxide and/or 1-hydroxyphospholane oxide.
  • the preferred salts are the salts of 1-hydroxydihydrophosphole oxides of the formula (Ia) or formula (Ib) and salts of 1-hydroxyphospholane oxides of the formula (II) ##STR1## where
  • flame-retardant salts which are particularly suitable for the purposes of the invention are the metal salts of 1-hydroxy-3-alkyl-2,3-dihydro-1H-phosphole 1-oxide, 1-hydroxy-3-methyl-2,5-dihydro-1H-phosphole 1-oxide, 1-hydroxy-2,3-dihydro-1H-phosphole 1-oxide, 1-hydroxy-2,5-dihydro-1H-phosphole 1-oxide, 1-hydroxy-1H-phospholane 1-oxide and 1-hydroxy-3-methyl-1H-phospholane 1-oxide and also mixtures of these salts.
  • the metal which provides the cations of these salts is preferably a metal of the second and third main or sub groups of the Periodic Table of the Elements, particularly Group IIA, Group IIB, and/or Group IIIA, e.g. the alkaline earth metal salts (Group IIA), especially magnesium.
  • Zinc is the preferred metal of Group IIB
  • aluminum is the preferred metal of Group IIIA. Particularly good results have been obtained with the aluminum salts.
  • the salts can be prepared from 1-hydroxydihydrophosphole oxides and 1-hydroxyphospholane oxides in aqueous solution by reaction with the corresponding metal carbonates, metal hydroxides or metal oxides.
  • 1-hydroxydihydrophosphole oxides and/or 1-hydroxy-phospholane oxides are generally dissolved in water and advantageously admixed with stoichiometric amounts of the corresponding metal hydroxide, metal carbonate or metal oxide by stirring.
  • the reaction mixture is then generally heated, preferably to a temperature from 30 to 150° C., in particular 70 to 110° C., and stirred for several hours.
  • the reaction times range from a few hours (at least 10 hours) to several days (1 to 7 days).
  • the reaction mixture is worked up by conventional methods (cooling, filtration with suction, washing, drying, etc.).
  • the starting compounds are known in the art (e.g. 1-hydroxydihydrophosphole oxides) and are obtainable by known methods (e.g. from the 1-chlorodihydrophosphole oxides), which can be prepared for example as described in EP-A1-0452755.
  • the 1-chlorodihydrophosphole oxides can be hydrogenated to prepare the 1-hydroxyphospholane oxides.
  • the salts of this invention are generally thermally stable. They do not decompose the polymers on incorporation into them and do not adversely affect the processing to make the molding material, notwithstanding the use of elevated temperature processing conditions such as temperatures of at least 250° C.
  • the salts are essentially non-volatile under the customary manufacturing and processing conditions for thermoplastics (including elevated temperature conditions such as those mentioned above). They exhibit excellent flame retardancy.
  • the preferred plastic (herein also referred to as the polymer) is moldable and hence is essentially thermoplastic or of such low crosslink density that it can be melted and, if necessary, remelted without substantial change in the polymer structure.
  • Preferred plastics are condensation polymers such as polyesters and/or polyamides, for example nylon 46 or nylon 66 in the case of polyesters, and polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) in the case of preferred polyesters.
  • Polyamides and polyesters which can be used for the purposes of this invention are described for example in "Ullmann's” encyclopedia of industrial Chemistry, ed. Barbara Elvers, Vol. A21, chapter Polyamide (p. 179-205) and chapter “Polyesters (p. 227-251), VCH, Weinheim-Basel-Cambridge-New York 1992", incorporated herein by reference.
  • the amount of salt to be added to the polymer can vary within wide limits. In general, 5 to 30% by weight, preferably 10 to 20% by weight, are used, based on the polymer. The most suitable amount depends on the nature of the polymer and the nature of the salt used and can be readily ascertained by experimentation.
  • the flame-retardant salts can be used in various physical forms, depending on the nature of the polymer used and the desired properties. For instance, they can be ground to a finely divided form, for example for achieving a better dispersion in the polymer. If desired, it is also possible to use mixtures of various salts.
  • a flame-retardant salt can be incorporated into the polymer by a variety of known techniques.
  • "incorporating" the flame-retardant salt is thus not limited to any specific physical combination procedure or any particular phase of the polymer (molten, solid, pre-polymeric, etc.), but chemical incorporation (where, for example, a salt is linked into the polymer molecule) is not required; physical combinations of the salt and the polymer provide the desired benefits of this invention.
  • the polymer and the salt are mixed together; the polymer portion of the resulting mixture is melted in a compounder (a twin-screw extruder, for example); and the flame-retardant salt is homogenized in the polymer melt.
  • a compounder a twin-screw extruder, for example
  • the melt can be extruded, cooled and granulated.
  • the salt can also be metered directly into the compounder.
  • the salt in a form which is as compatible as possible with the polymer or plastic to be rendered flame retardant.
  • Such especially convenient forms include particulate plastic masses (particularly plastic granules) containing a minor amount of the salt or particulate (e.g. granular) masterbatches containing much higher percentages of salt (e.g. 30 to 80 or 90% by weight, based on the weight of the masterbatch).
  • the flame-retardant salt can be mixed into a polymer which lacks flame-retardant properties.
  • finished granular polymer containing the desired amount of flame-retardant salt e.g. 5 to 30% by weight of the polymer
  • a mass of such granular polymer can be processed directly on an injection molding machine.
  • a mixture can first be melted in an extruder, granulated, and processed after drying.
  • Incorporation of the flame-retardant salts can also be accomplished in condensation-polymerized plastics, e.g. in polyesters, during an early stage in the manufacture of the product, e.g. during the polycondensation.
  • the product which results is a flame-retardant plastic or polymer, typically in the form of a moldable material or in the form of a material which has already been shaped.
  • the flame-retardant plastic or polymer can contain, in addition to a flame-retardant salt or mixture of salts, a variety of conventional components which provide or alter the color, the stability, the physical properties of the plastic, and the like.
  • the polymers can also have added to them fillers and reinforcing materials such as glass fibers, glass balls or minerals such as chalk, UV stabilizers, lubricants, colorants, pigments, nucleating agents, antistatic agents, or various combinations of these components.
  • the plastics such as polyamides and polyesters, rendered flame-retardant using one of the aforementioned flame-retardant salts are typically in the form of a molding material and thus are useful for manufacturing shaped articles, which broadly includes films, coatings on substrates, filaments and fibers as well as more massive three-dimensional objects.
  • Typical molding procedures useful in this invention include injection, extrusion or press molding.
  • shaped objects made in accordance with this invention can include a wide variety of electrical, electronic, and mechanical (including electro-mechanical) components. Examples of such components include:
  • Coil formers Transformers, relays, switches, plug connectors, motors and motor parts (rotors, bearing plates, etc.), molded interconnection devices (MIDs), bases (e.g. SIMM bases), mechanical components in electrical and household appliances, for example gearwheels, levers, camshafts, spacers, hinges, sliding bearings, housings, coverings, sheathings and coatings of electrical devices and appliances, for example capacitor housings, relay housings, capacitor covers, cable sheathings.
  • MIDs molded interconnection devices
  • bases e.g. SIMM bases
  • mechanical components in electrical and household appliances for example gearwheels, levers, camshafts, spacers, hinges, sliding bearings, housings, coverings, sheathings and coatings of electrical devices and appliances, for example capacitor housings, relay housings, capacitor covers, cable sheathings.
  • shaped articles include plugs, mounts, housings, coverings, sheathings, overcoatings. Coatings can be applied to a variety of known substrates.
  • flame-retardant salts can also be included in coatings such as fire protection coatings, especially fire protection coatings for plastics such as polyoxymethylene, polyester or polyamide.
  • the invention accordingly also provides for the use of the flame-retardant salts as a constituent of coatings, especially of fire protection coatings.
  • the present invention accordingly also provides for the use of salts of 1-hydroxydihydrophosphole oxides and/or 1-hydroxyphospholane oxides in coatings, especially fire protection coatings.
  • the phosphorus compounds were mixed with the polymer and incorporated on a commercially available twin-screw compounder.
  • customary glass fibers for polyester were metered into the melt.
  • the melt temperatures during the compounding were about 250° C. in the case of polybutylene terephthalate (PBT).
  • the test specimens were produced on an injection molding machine to ISO 7792-2.
  • Test specimens of each mixture were used to determine the UL 94 (Underwriters Laboratories) fire resistance classification on test specimens 1.2 mm in thickness and the breaking strength and breaking extension by the method of ISO 527.
  • UL 94 Underwriters Laboratories

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
US08/810,656 1996-03-04 1997-03-03 1-hydroxydihydrophosphole oxides and 1-hydroxy-phospholane oxides, preparation thereof and use thereof as flame retardants Expired - Fee Related US6087423A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19608011A DE19608011A1 (de) 1996-03-04 1996-03-04 Salze von 1-Hydroxy-dihydrophospholoxiden und 1-Hydroxy-phospholanoxiden und ihre Verwendung als Flammschutzmittel
DE19608011 1996-03-04

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US6087423A true US6087423A (en) 2000-07-11

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Country Status (7)

Country Link
US (1) US6087423A (fr)
EP (1) EP0794191B1 (fr)
JP (1) JPH09278784A (fr)
KR (1) KR970065547A (fr)
CN (1) CN1168381A (fr)
BR (1) BR9701157A (fr)
DE (2) DE19608011A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6252108B1 (en) * 1997-08-07 2001-06-26 Ticona Gmbh Method for producing aluminium salts of cyclic phosphinic acid
US6307097B1 (en) * 1997-05-20 2001-10-23 Ticona Gmbh Method for producing aluminum salts of cyclic phosphinic acids
US6344158B1 (en) 1999-01-30 2002-02-05 Clariant Gmbh Flame retardant combinations for thermoplastic polymers II
US6509401B1 (en) 1997-08-29 2003-01-21 Clariant Gmbh Synergistic flame retardant combination of salts of 1-hydroxy-dihydrophosphole oxides and/or 1-hydroxyphospholane oxides and nitrogen compounds for use in polymers
US20070048622A1 (en) * 2005-08-24 2007-03-01 Jae-Gu Yoon Organic electrolytic solution and lithium battery using the same
US9276290B2 (en) 2011-03-24 2016-03-01 Samsung Sdi Co., Ltd. Electrolyte for rechargeable lithium battery and rechargeable lithium battery comprising same
US10723833B2 (en) 2015-11-13 2020-07-28 Icl-Ip America Inc. Reactive flame retardants for polyurethane and polyisocyanurate foams

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19708726A1 (de) 1997-03-04 1998-09-10 Hoechst Ag Flammgeschützte Polymerformmassen
DE19708725A1 (de) 1997-03-04 1998-09-10 Hoechst Ag Aluminiumsalze von Alkyl-hydroxymethylphosphinsäuren
DE19708724A1 (de) 1997-03-04 1998-09-10 Hoechst Ag Aluminiumsalze von Alkyl-1-alkoxyethylphosphinsäuren
MY117653A (en) 1997-06-13 2004-07-31 Polyplastics Co Flame-retardant thermoplastic polyester resin composition
TR200201863T2 (tr) * 2000-01-21 2002-11-21 Ticona Gmbh Motorlu araçların motor bölmesinde termoplastik malzemeleri yapı elemanlarının üretimi.
DE10305548A1 (de) * 2003-02-10 2004-08-26 Basf Ag Flammgeschützte Kunststoffformteile
JP5243006B2 (ja) * 2006-12-04 2013-07-24 三菱エンジニアリングプラスチックス株式会社 難燃性ポリアミド樹脂組成物および成形品
JP5468944B2 (ja) 2010-03-12 2014-04-09 矢崎総業株式会社 押出しフレキシブルフラットケーブル
US10093801B2 (en) 2013-12-12 2018-10-09 Italmatch Chemicals S.P.A. Halogen-free flame retardant polyamide moulding compositions with increased glow wire and fire resistance

Citations (9)

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BE700042A (fr) * 1966-06-18 1967-12-01
DE2252258A1 (de) * 1972-10-25 1974-05-09 Hoechst Ag Schwerentflammbare thermoplastische polyester
DE2447727A1 (de) * 1974-10-07 1976-04-08 Hoechst Ag Schwerentflammbare polyamidformmassen
DE2915116A1 (de) * 1978-04-13 1979-10-25 Pennwalt Corp Flammwidrig gemachte polyester- und polyamidharze
US4208322A (en) * 1978-04-13 1980-06-17 Pennwalt Corporation Polyester-polyamide resins flame retarded by poly(metal phosphinate)s
US4221874A (en) * 1978-06-07 1980-09-09 Monsanto Company Phospholane oxide containing polymers
US4268432A (en) * 1976-06-21 1981-05-19 Imperial Chemical Industries Limited Polyamide compositions
US4471080A (en) * 1982-02-09 1984-09-11 Saffa S.P.A. Process for making self-extinguishing, by means of red phosphorus, synthetic thermoplastic materials and products so obtained
EP0699708A2 (fr) * 1994-08-31 1996-03-06 Hoechst Aktiengesellschaft Masses à mouler ignifugées à base de polyester

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DE4012489A1 (de) 1990-04-19 1991-10-24 Bayer Ag Verfahren zur herstellung von 1-halogen-1-oxophospholenen
DE19608006A1 (de) * 1996-03-04 1997-09-11 Hoechst Ag Salze von phosphonigen Säuren und deren Verwendung als Flammschutzmittel in Kunststoffen
DE19645125A1 (de) * 1996-11-04 1998-05-14 Hoechst Ag Verfahren zur Herstellung von Aluminiumsalzen organischer Phosphorsäuren

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Publication number Priority date Publication date Assignee Title
BE700042A (fr) * 1966-06-18 1967-12-01
DE2252258A1 (de) * 1972-10-25 1974-05-09 Hoechst Ag Schwerentflammbare thermoplastische polyester
US3900444A (en) * 1972-10-25 1975-08-19 Hoechst Ag Flame resistant thermoplastic polyesters
DE2447727A1 (de) * 1974-10-07 1976-04-08 Hoechst Ag Schwerentflammbare polyamidformmassen
US4036811A (en) * 1974-10-07 1977-07-19 Hoechst Aktiengesellschaft Flame retarding polyamide molding compositions
US4268432A (en) * 1976-06-21 1981-05-19 Imperial Chemical Industries Limited Polyamide compositions
DE2915116A1 (de) * 1978-04-13 1979-10-25 Pennwalt Corp Flammwidrig gemachte polyester- und polyamidharze
US4208322A (en) * 1978-04-13 1980-06-17 Pennwalt Corporation Polyester-polyamide resins flame retarded by poly(metal phosphinate)s
US4221874A (en) * 1978-06-07 1980-09-09 Monsanto Company Phospholane oxide containing polymers
US4471080A (en) * 1982-02-09 1984-09-11 Saffa S.P.A. Process for making self-extinguishing, by means of red phosphorus, synthetic thermoplastic materials and products so obtained
EP0699708A2 (fr) * 1994-08-31 1996-03-06 Hoechst Aktiengesellschaft Masses à mouler ignifugées à base de polyester

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Title
Journal of Polymer Science: Part A 1, vol. 6, 1975 1990 (1968); Metal Coordination Polymers. I. Synthesis and Thermogravimetric Analysis of Beryllium Phosphinate Polymers; P.J. Slota, Jr., L.P. Freeman, and N.R. Fetter. *
Journal of Polymer Science: Part A-1, vol. 6, 1975-1990 (1968); Metal Coordination Polymers. I. Synthesis and Thermogravimetric Analysis of Beryllium Phosphinate Polymers; P.J. Slota, Jr., L.P. Freeman, and N.R. Fetter.

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6307097B1 (en) * 1997-05-20 2001-10-23 Ticona Gmbh Method for producing aluminum salts of cyclic phosphinic acids
US6252108B1 (en) * 1997-08-07 2001-06-26 Ticona Gmbh Method for producing aluminium salts of cyclic phosphinic acid
US6509401B1 (en) 1997-08-29 2003-01-21 Clariant Gmbh Synergistic flame retardant combination of salts of 1-hydroxy-dihydrophosphole oxides and/or 1-hydroxyphospholane oxides and nitrogen compounds for use in polymers
US6344158B1 (en) 1999-01-30 2002-02-05 Clariant Gmbh Flame retardant combinations for thermoplastic polymers II
US20070048622A1 (en) * 2005-08-24 2007-03-01 Jae-Gu Yoon Organic electrolytic solution and lithium battery using the same
US8062796B2 (en) * 2005-08-24 2011-11-22 Samsung Sdi Co., Ltd. Organic electrolytic solution and lithium battery using the same
US9276290B2 (en) 2011-03-24 2016-03-01 Samsung Sdi Co., Ltd. Electrolyte for rechargeable lithium battery and rechargeable lithium battery comprising same
US10723833B2 (en) 2015-11-13 2020-07-28 Icl-Ip America Inc. Reactive flame retardants for polyurethane and polyisocyanurate foams
US10730995B2 (en) 2015-11-13 2020-08-04 Icl-Ip America Inc. Reactive flame retardants for polyurethane and polyisocyanurate foams

Also Published As

Publication number Publication date
CN1168381A (zh) 1997-12-24
JPH09278784A (ja) 1997-10-28
KR970065547A (ko) 1997-10-13
DE59710003D1 (de) 2003-06-12
DE19608011A1 (de) 1997-09-11
EP0794191A1 (fr) 1997-09-10
EP0794191B1 (fr) 2003-05-07
BR9701157A (pt) 1998-12-15

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